Method of producing higher alkyl aromatic sulphonates



Patented Mar. 30, 1943 METHOD OF PRODUCING HIGHER ALKYL AROMATICSULPHONATES Lawrence H. Flett, Hamburg, N. Y., assignor to AlliedChemical & Dye Corporation, a corporation of New York No Drawing.Application November 20, 1940, Serial No. 366,384

11 Claims.

alkyl aromatic sulphonates from halogenated non-aromatic hydrocarbonmixtures by condensation with aromatic compounds with the aid ofaluminum chloride as a condensation catalyst, followed by sulphonationof the condensation product.

An object of the invention is to provide improvements in the method ofproducing higher alkyl aromatic sulphonates from halogenatednon-aromatic hydrocarbons, on the one hand, and aromatic compounds ofthe :class consisting of hydrocarbons, chlorhydrocarbons and alkoxysubstituted hydrocarbons of the benzene and naphthalene series, on theother hand, by condensation with the aid of aluminum chloride as acondensation catalyst, followed by sulphonation, whereby sulphonatedproductsare obtained having improved properties.

Another object of the invention is to provide improvements in the methodof producing higher alkyl aromatic sulphonates from halogenatednon-aromatic hydrocarbons and aromatic compounds of the class referredto above by condensation with the aid of aluminum chloride as acondensation catalyst, followed by sulphonation, whereby sulphonatedproducts are obtained which are sufliciently free from coloredby-prodnets to be commercially acceptable.

.A further object of the invention is to provide improvements in themethod of producing higher alkyl aromatic sulphonates fromv halogenatednon-aromatic hydrocarbons-and aromatic compounds of the class referredto above by condensationvwith the aidof aluminum chloride as acondensation catalyst, followed by sulphonation, whereby vsulphonatedproducts are obtained having improved surface active, detergent, wettingand penetrating action. I An additional object of the invention is toprovide improvements in the method of producing higher alkyl aromaticsulphonates of the benzene .series from chlorinated kerosene fractionsof petroleum distillates and aromatic hydrocarbons of the benzene seriesby condensation withthe aid of aluminum chloride as a condensationcatalyst,

followed by sulphonation, whereby sulphonated matic nucleus represent adesirable class of products, particularly in the form of their alkalimetal and organic ammonium salts, for use as substitutes for soaps inview of certain of their advantageous properties; as for example,resistance to acid and hard water, washing and lathering ability in hardwater and sea water, and freedom from hydrolysis.

One method for producing alkyl aromatic sulphonates involveshalogenating a mixture of non-aromatic hydrocarbons, condensing theresulting mixture of halogenated hydrocarbons with the aromatic compoundof the type desired in the final product, sulphonating the resultingcondensation product, and recovering the sulphonated product, afterconversion to a salt when desired. Thus, one method of producing analkyl benzene sulphonate product comprises chlorinating a petroleumdistillate, condensing the resulting mixture of alkyl chlorides-withbenzene with the aid of a small amount of anhydrous aluminum chloride asa catalyst, separating the resulting mixture of alkyl benzenes from thecondensation mass, sulphonating the mixture of alkyl benzenes to producea mixture of alkyl benzene sulphonates, neutralizing the sulphonationreaction mixture with aqueous sodium hydroxide solution, and recoveringthe resulting mixture of sodium alkyl benzene sulphonates.

The products obtained by this process have the disadvantages that theyare highly colored and have insufficient cleansing ability to becommercially acceptable as substitutes for soap in the usual householdand textile uses. In general, soap substitutes which are colored are notacceptable because they stain goods treated with them and leave depositswhich later develop stains in the goods. Furthermore, their appearanceis unattractive-and they dissolve in water to form undesirably coloredsolutions. While in some cases the color of the products can be improvedby treatment with reducing agents, as for example zinc and acetic acidor zinc dust, or with oxidizing agents, -such treatments are costly andresult in yield losses while the improvement in color which is producedis generally of a temporary nature.

According to the present invention alkyl aromatic sulphonates ofcommercially acceptable color and of sufficient detergent, wetting andsurface active action to be commercially acceptable as soap substitutesare obtained by incorporating into the process of producing the alkylaromatic sulphonates the improvements hereinafter ,disclosed and claimedin the appended patent claims.

This application is a continuation-in-part of my application Serial No.186,231, filed January 21, 1938, now U. S. P. 2,223,364, which is acontinuation-in-part of my application Serial No.

resulting chlorkerosene mixture 93,719, filed July 31, 1936, now U. S.P. 2,195,409.

As disclosed in my application Serial No. 186,231, I have found thathigher alkyl benzene sulphonates which in the form of solids are a paleyellow to white color, dissolving in water to form clear, almostcolorless solutions which possess excellent washing and wettingproperties, are obtained in good yield bychlorinating a kerosenefraction of petroleum distillate to an extent such that the resultingchlorination reaction mixture contains an amount of organically combinedchlorine substantially corresponding with 100 to 140 per cent completemonochlorination of the kerosene hydrocarbons, reacting benzene with thecomprising higher alkyl monochlorides together with some polychloridesand unchlorinated kerosene) in the presence of an amount of anhydrousaluminum chloride equal to 5 per cent to per cent of the weight of thechlorkerosene mixture at temperatures not exceeding 110 C., separatingthe lightcolored oily mixture of alkyl benzenes from the dark-coloredsludge produced as a by-product,

distilling ofl excess benzene from the mixture of albl benzenes,reacting the mixture of alkyl benzenes with a sulphonating agent, andneutralizing the sulphonated product with sodium hydroxide in aqueoussolution. The oily mixture of alkyl benzenes obtained as an intermediateproduct by this procedure are but faintly colored, and the sulphonatedproducts without further purification-are sufllciently free fromobjectionable colored by-products to be acceptable for commercial saleand use.

In the practice of the present invention in accordance with onepreferred method of procedure, a non-aromatic hydrocarbon mixture, moreparticularly one containing at least 10 carbon atoms, and preferablyabout 12 to about carbon atoms per molecule, is halogenated to an extentsuch that the resulting halogenation reaction mixture contains an amountof organically combined halogen substantially corresponding with 75 percent to 175 per cent complete monohalogenation of the originalnon-aromatic hydrocarbon mixture; the resulting mixture of halogenatedhydrocarbons (herein generically designated by the term alkyl halidemixture") is reacted with the aromatic compound to be alkylated, in thepresence of an amount of aluminum chloride equal to less than 5 per centof the weight of th alkyl halide mixture (generally 4 per cent or lessof the weight of the alkyl halide mixture) and at a temperature whichdoes not exceed 130 0.; the condensation reaction mass is permitted tostratify into an upper layer containing mainly a mixture of alkylaromatic compounds and a lower layer of darkly colored sludge; the upperlayer is removed from the lower layer and is subjected to furthertreatment at a temperature not exceeding 130 C. with' an additionalamount of aluminum chloride, the total amount of aluminum chloride beingat least 5 but not more than 20 per cent of the weight of the alkylhalide mixture, the resulting reaction mass is permitted to stratifyinto an upper layer containing mainly a mixture of alkylaromaticcompoundsand a lower layer of darkly colored sludge; the upper layer isremovedfrom the lower layer, and the mixture of alkyl aromatic compoundsis subjected to sulphonation. The resulting mixture of sulphonic acidsis preferably converted into a mixture of their corresponding salts. Ifinorganic salts are simultaneously formed, they may be left in themixture of said sulphonic acid salts, or they may be separatedtherefrom, as the use of the product may determine.

I have found, in accordance with one feature of the present invention.that the use of a total amount of aluminum chloride equal to 5 to 20 percent of the weight of the alkyl halide mixture at a temperature notexceeding 130 0., in conjunction with separation of the mixed alkylaromatic compounds from the sludge formed as a by-product, results in aproduct which when sulphonated has superior properties with respect tocolor and surface active action, as compared with products obtained witha smaller amount of aluminum chloride and/or at higher temperatures. Ihave further found, in accordance with another feature of the presentinvention, that the halogenation of the non-aromatic hydrocarbon mixtureto an extent such that the resuling halogenation reaction mixturecontains an amount of organically combined halogen substantiallycorresponding with 75 per cent to 1'75 per cent completemonohalogenation of the. original non-aromatic hydrocarbon mixture,results in commercially satisfactory yields of alkyl aromaticsulphonates notwithstanding the use of the relatively large amounts ofaluminum chloride employed in accordance with the present invention,especially when amounts of aluminum chloride not exceeding 15 per centof the weight of the alkyl halide mixture are employed.

It was heretofore known to condense an alkyl halide with an aromatichydrocarbon with the aid of anhydrous aluminum chloride as a catalyst,but in order to avoid low yields of alkyl aromatic product the amount ofaluminum chloride employed was limited to amounts lust adequate toeffect the condensation, generally below 4 per cent of the weight ofalkyl halide or alkyl halide mixture. When a halogenated fraction ofpetroleum distillate containing an amount of organically combinedhalogen substantially correspond-' ing with 75 per cent to 175 per centcomplete monohalogenation of the hydrocarbon mixture, as for examplechlorinated kerosene containing an amount of organically combinedchlorine corresponding with about per cent monochlorination of thekerosene is condensed with an aromatic hydrocarbon, for example,benzene, toluene, etc., with the aid of anhydrous aluminum chloride in acatalytic amount, for example, less than 4 per cent by weight of thealkyl halide mixture, th resulting alkyl aromatic condensation productsare inferior in quality and the sulphonated mixtures derived therefromare highly colored.

The presentinvention comprehends a procedure in which the condensationof the alkyl halide mixture with the aromatic constituent is'carried outat a temperature below C. with a small amount of anhydrous aluminumchloride (4 per cent or less of the weight of the alkyl halide mixture)and the resulting condensation product is then subjected to furthertreatment at a temperature below 130 C. with additional anhydrousaluminum chloride, to effect the improved result of the presentinvention.

The invention will be illustrated by the following specific examples. Itwill be realized by those skilled in the art that the invention is notlimited thereto except as indicated in the appended patent claims. Theparts are by weight, the temperatures are in degrees centigrade and thepressure is atmospheric, unless otherwise indicated. For convenience aproduct obtained by chlorinating a kerosene fraction of petroleum istermed "keryl chloride and the product obtained by condensing the kerylchloride with toluene, forexample, is termed keryl toluene."

EXAMBLE 1 ample 1 of my U. S. Patent No. 2,223,364 to which a smallamount of iodine (0.05 part per 100) was added as a halogenatingcatalyst, was chlorinated by passing therethrough a stream of chlorinegas while the mixture was maintained at about 60 until organicallycombined chlorine in the mixture corresponded to about 125 per cent ofthe amount theoretically required for complete monochlorination. 150partsof this chlorinated oil were added in a small stream to a wellagitated mixture of 100 parts of benzene and 6 parts of anhydrousaluminum chloride. The reaction mixture was maintained throughout theaddition from about 30 to about 60 and, after the addition of thechlorinated oil, was stirred for about 6 hours, and then allowed tostand for about 10 hours. The upper layer of oil was separated from thelower tarry mass, and heated to remove thereother alkyl aromaticsulphonates disclosed in the present application and especially thosedisclosed in Examples 1 to 5 inclusive of my United States Patent2,223,364. Instead of carrying out the process in two stages, asdisclosed in Parts 1 and 2 of Example 1, the process may-be carried outin three or more stages. Further, the invention includes procedures inwhich residual benzene or residual other aromatic'compounds employed asstarting material are not removed by distillation prior to theadditional treatment with aluminum chloride, and/or lower boilingconstituents are not removed from the alkyl'aromatic compounds resultingfrom the aluminum chloride treatment.

from unreacted benzene by distillation. The resulting product was a darkbrown oil consisting mainly of nuclearly alkylated benzenes in which thealkyl groups averaged about 13 to 14 carbon atoms.

Part 2.-110 parts of the dark brown oil were agitated with 10 parts ofanhydrous aluminum chloride and 70 parts of kerosene as a diluent, forabout 3 hours while maintaining the temperature at about 55 to about 60.The mixture was then allowed to stand and to separate into two layers.The upper layer of yellow oil was decanted from the lower layer of blacktarry matter. After being washed with about half its volume of water,the decanted oil was distilled until all volatile material thereinboiling below 120 at 5 mm. mercury was removed. The residual oil was apale yellow mobile liquid weighing 97 parts. For the production of asulphonated product, 1 part of the resulting oil was mixed with about1.1 to about 1.3 parts of 26 per cent oleum at a temperature of 5 to 15and was further treated to obtain the sulphonated product in the form ofthe sodium salt by pouring the sulphonation mixture (when 1 part of atest portion, after neutralizing with sodium hydroxide, was soluble in20 parts I of water) into approximately 12.5 parts of an icewatermixture, neutralizing the resulting solution to Brilliant yellow andCongo red papers with concentrated aqueous caustic alkali (e. g., a 50%aqueous solution of sodium hydroxide) and evaporating the neutralizedsolution to dryness on a rotary drum drier. The dry sulphonated productwas a faintly yellow, friable solid which dissolved readily in water togive clear, substantially colorless solutions having excellent wettingand detergent properties.

When the dark brown oil, resulting from the procedure of Part 1 of thisexample, was sulphonated and recovered in the same manner, the resultingproduct was a dark brownish solid which dissolved in water to formbrownish colored solutions which, on the basis of equal concentrationsof alkyl aromatic sulphonates, possessed inferior wetting and washingproperties as compared with the product obtained by the furthertreatment in accordance with Part 2 of this example.

The procedure of Example 1 may be applied in a similar manner to thepreparation of the rine.

ExAMPLE 2 1200 grams of a kerosene fraction of Pennsylvania petroleumdistillate, having a boiling range of approximately to 280 and aspecific gravity of 0.7888 at 24 which on the basis of its source andproperties was considered to be a mixture orhydrocarbons (mainly openchain aliphatic hydrocarbons) having an average molecular carbon contentof 13 to 14 carbon atoms and a range from about 11 to about 16 carbonatoms per molecule, were chlorinated by passing therethrough chlorinegas at such a rate that about 4.25 grams per minute reacted with thekerosene. During the chlorination, the kerosene was agitated andmaintained at a temperature between 60 and 62. After about 2 hours ofchlorination, a current of air was passed through the agitated charge tosweep out dissolved hydrogen chloride and chlograms and had a specificgravity of 0.917 at 24.

Four condensations, which were alike in all respects except with regardto the treatment with anhydrous aluminum chloride, were made from theforegoing chlorinated kerosene mixture (keryl chloride) In run #1,608grams toluene and 27.4 grams anhydrous aluminum chloride wereagitated, and 304 grams of the chlorinated kerosene mixture were run inover a period of about 20 minutes without heating or cooling themixture. The reacting mass was then warmed to 45 and agitated at 44 to46 for 1% hours.

In runs #2, #3 and #4, this procedure was followed, but 9 grams insteadof 27.4 grams of anhydrous aluminum chloride were used in each case.

From this point, the four condensations differed as follows:

Runs #1 and #4 were allowed to stand for about 16 hours before the nextprocess step, which is described below.

Run #2 was treated with an additional 18.2 grams anhydrous aluminumchloride, and agitated at 44 to 46 for 1 /2 hours and allowed thereafterto stand for about 16 hours.

Run #3 was allowed to stand /2 hour; a tarry layer which separated onstanding was removed and discarded; agitation was resumed and 9- gramsof additional anhydrous aluminum chloride were added to the mass whichwas then agitated for 1 /2 hours at 44 to 46; the mass was again allowedto stand /2 hour; a tarry layer was again removed; agitation was thenresum d and another 9 grams anhydrous aluminum chlo ride were added; themass was then stirred for 1% hours at 44 to 46 and allowed to standabout 16 hours.

From this point, each of the runs was treated in the same manner.

after the 16 hour period of standing, a seba- The charge had gained inweight by 257 rated lower tarry layer of the mixture was removed, andthe upper layer of oily liquid was distilled, flrstgat atmosphericpressure to a vapor temperature of: 125 to remove most of the untion. Inthe event that a solution of the dry product was less colored than thatof the standard light-colored solution, a 100cc. sample of the.

latter solution was diluted with water and comreacted toluene and thenat reduced pressure to 5 pared with 100 cc. of solution of the sampleuna vapor temperature oi 80 at 4 millimeters of dergoing examinationuntil the color of the dimercury absolute pressure. In each run, thereluted standard solution was substantially equal sidual distilland wasa light-amber ofl compristo that of the sample, and the color of thesample ing a mixture of'alkyl toluene condensation prodwas expressed interms of the percentage of the ucts. The residual distillands from runs1, 2, 3 l sample volume with respect to the volume of and 4, in theorder named, weighed 223, 238, 22 7 the diluted standard solution. Thus.a product and 284 grams, respectively. is said to have a color of 195%,when on starting Each of the four residual distillands compriswith asolution of the same concentration as ingmixtures of alkyl toluenecondensation prodthe standard solution it is necessary to dilute thenets was then sulphonated by the following pro- 1 solution to 1.95 timesits original volume before cedure. 100 grams of the distilland wereagitated its color matches that of the standard; similarly at roomtemperature for about hour with 10 a product is said to have a color of75 per cent cc. of 100 per cent sulphuric acid. After stand .Wh n i inecessary o ilute the standard soluing for about /2 hour, the acid layerwas drawn tion to 1.33 times its original volume before its oil anddiscarded. The refined olly'material was 1 matches that Of the p thenagitated and sulphonated by adding 100 cc. Wetting power was measured bydetermining of sulphuric acid monohydrate at room temperathe length oftime necessary to wet out a standture during 10 to 20 minutes, and thenagitating ard sized sample of standard fabric with a solufor one hour at55 to 60. After adding 2 cc. of 'tion of the product at definitetemperature and water to the suiphonation mixture and agitating 5concentration. 500 cc. of a 0.2 per cent-solution briefly, the mass wasallowed to stratify for one of the product to be tested were placed in a600 hour. Two layers formed. The upper sulphonic cc. beaker andmaintained at 50. A No. 10 canacid layer was separated from the lowerspent vas disk 1 inch in diameter was placed on the acid layer which wasdiscarded. The sulphonic surface of the solution and immediately cuppedacid layer was poured onto about 250 grams of in a long-stem invertedfunnel and forced below cracked ice and the resulting solutionneutralthe liquid level to a depth of 5 to 6 centimeters. ized.Suflicient sodium sulphate was added to The time from cupp until e diskcommenced adjust the'inorganic salt content of the solute to fallout ofthe funnel was measured and is to 60 per cent and the resultingsolution, was gi enas e wetting time. dried on a double drum dri r, Thewool-washing tests were conducted as fol- The four detergent preparationso obt n lows: Asample of wool cloth was uniformly soiled were testedfor solution color, wetting power and with lamp b a Willow and mineralIt was detergency for dirty wool. then cut into pieces of approximatelyequal size The results are given in the table. (4 inches by 4-inches)which were washed in a The method of comparing colors of solutions 40Launderometer in 200 cc. of solution of product and determining thepercentage values of colors for a Standard period of 30 minutes at Twoas given in the table was as follows: 100 cc. of a series of washingswere made. In one series, the 5 per cent solution of the dry productwere placed solutions used for the washing tests contained in arectangular 4-ounce clear glass bottle. The 0.1% of product dissolved indistilled water, and solution was compared with a standard light- 45 inthe other series, the solutions contained colored solution of the sameconcentration by I o product dissolved in Water 0f hard- V reflectedlight from a white background. The ness (American scale). The degree ofwashing solution of the sample undergoing examination was determined bytaking readings of reflected was diluted with water until the color ofthe dllight (brightness) from the washed cloth with a luted solution wassubstantially equal to that of Pfaltz and Bauer universal photoelectricreflecthe standard solution and the color wa expressed tometer. Thereadings determined increased in terms of the percentage which thevolume of brightness which was measured by the difierence the dilutedsolution of the sample represented in the readings obtained with thereflectometer with respect to the volume of the standard soluon thesoiled cloth before and after washing.

TABLE Data on preparation and testing of keryl toluene sulphonatesproduced with diflerent amounts of anhydrous aluminum chlorideDctergcncy expressed as Aluminum chloride used (expressed as percentbrightness increa e (orig. M (L of i based on kcryl chloride) 0 l rhrigl'itgu'ss of soiled wool .n or 0 was 231222;; detergent Wetting timeduccd per iloproduct 0187 concn gram oi kcro- During 0011- Forsubsequent T t l 0.1% concn. i 5 hard semconsumed) dcnsaiion treating oa in soft water water I Per cent Per cent Per cent iwz'nutes l 8 4 9 90. 63 21 3B 2 961 3 6% without first 9 110 0.77 22.5 38

sepg. tar irom catalyst. 3. 920 3 Two 3% incre- 9 0.68 22 37 ments withintermediate tar A scparation.- 4 101s 3 a 105 0.10 14 29 Data on yieldpresented in the table show that the highest yields of organic detergnetmaterial were obtained in run #4 in which 3% aluminum chloride was usedto eflect the condensation and no subsequent treatment with aluminumchloride was carried out. Evidently 3% aluminum chloride is adequate toinsure completion of the condensation reaction of keryl chloride withbenzene. Treatment with more than 3% aluminum chloride as in runs 1, 2and 3 causes the yield of organic detergent material to be decreased byabout The surprising discovery has been made that this loss in yield ismore than compensated for by improvement in detergent quality.

It is evident from the table that the detergent derived from acondensation product, made with an amount of aluminum chloride equal to3 per cent of the weight of chlorinated kerosene used in thecondensation is characterized by lesser washing action and darker colorthan the detergent which was made with an amount of aluminum chlorideequal to 9 per cent of the kerosene chloride used in the condensation;and that the inferiority of the former detergent can be overcome andavoided by treating the condensation reaction mass (made with 3%aluminum chloride) with an additional amount (6%) of aluminum chloride.This treatment with the additional amount of aluminum chloride may beeffected equally well with or without preliminary removal of spentcatalyst from the condensation reaction. The treatment with theadditional aluminum chloride is also equally effective as far as qualityof final detergent composition is concemed if the additional aluminumchloride is added all at one time or in increments with intermediateseparation of tarry sludges produced between additions of the saidincrements.

In the above examples the amount of aluminum chloride employed can beincreased up to 20 per cent of the weight of the alkyl chloride mixture,but amounts in excess of about per cent are not preferred for theobtainment of desirable yields.

It will be realized by those skilled in the art that changes may be madein the processes here- -inbefore described without departing from thescope of the invention.

The hydrocarbon mixtures which may be employed as starting materials inaccordance with the present invention are non-aromatic hydrocarbonmixtures, preferably aliphatic hydrocarbon mixtures, and especiallymineral oil distillates, containing from 10 carbon atoms to 30 carbonatoms. and preferably from 12 to 28 carbon atoms. The particular type ofhydrocarbon mixture employed will vary, depending upon the specific usefor which the product is designed and the particular aromatic nucleuswith which it is combined, as will be evident to those acquainted withthe art. (By the term "non-aromatic hydrocarbon mixtures as employedherein, I mean hydrocai bon mixtures containing essentially straightand/or branched open chain saturated hydrocarbons and/or alicyclichydrocarbons and which may contain other hydrocarbons but not more thanper cent of aryl hydrocarbonasuch as' petroleum, petroleum distillates,artificially or synthetically prepared mixtures, etc.)

As is well known in the art, petroleum distillates are mainly mixturesof aliphatic hydrocarbons, including both saturated acyclic aliphatichydrocarbons containing straight or branched carbon chains and cyclicaliphatic hydrocarbons,

preparation of products of the present invention,

mixtures of various halogenated derivatives of the said aliphatichydrocarbons (alkyl halides) are produced and the said mixtures of alkylhalides, when condensed with aromatic compounds, produce mixtures ofalkyl aromatic compounds, in which the alkyl groups correspond withaliphatic hydrocarbons of the petroleum distillate from which they wereproduced. Accordingly, when the mixtures of alkyl aromatic compounds aresulphonated, compositions are produced which contain mixtures ofsulphonated alkyl aromatic compounds differing from each other in thealkyl groups, which groups corre spond with the aliphatic hydrocarbonsof the mixture employed.

The preferred hydrocarbon mixtures employed in accordance with thepresent invention are exemplified by fractions of Pennsylvania andMichigan (Mount' Pleasant) petroleum distillates. These distillatesconsist essentially of open chain aliphatic (paraffinic) hydrocarbons alarge portion of which are probably relatively long carbon chains ratherthan more condensed molecules. as "of the Pennsylvania type, whetherderived from natural sources or derived by processing or by purificationof less favorable distillates from other. sources.

The halogenation of the non-aromatic hydrocarbon mixture may be carriedout by any well known process. The approximate extent of halogenationmay be determined by the increase in the weight of the hydrocarbonmaterial halogenated or by the increase in the specific gravity of themixture. Instead of chlorine, other halogens may be employed in theprocesses of the above examples, e. g., bromine, etc.

Various chlorination temperatures may be em ployed, for example,temperatures within the range 0 to 75 C., and preferably in theneighborhood of 50 to 60 C. The chlorination may be carried out with theaid of chlorine carriers, catalysts or adjuvants; as for example,phosphorus trichloride, iodine, sunlight, etc.

The aromatic compounds preferably employed in accordance with thepresent invention are the various aromatic hydrocarbons and their alkoxyand halogen derivatives, as for example benzene, toluene, xylene,diphenyl, naphthalene, monochlorbenzene, anisole, phenetole.

To effect the improved results of the present invention, the temperatureat which the mixed alkyl halides and the aromatic compounds arecondensed in the presence of the relatively large amounts of anhydrousaluminum chloride ought not exceed 130 C., and is. preferably betweenabout 20 and C. In general at temperatures below 80 0., thecondensations are slow, incomplete and cause lower yields of desiredcondense. tion products; while condensations effected at temperaturesabove C. result in composltions which comprise undesirable compoundsthat increase in amount and in undesirable properties as the temperatureof condensation in-' creases, until at temperatures above about C. thecompositionsare of little if any value for the manufacture ofcommercially acceptable alkyl aromatic sulphonates.

Such distillateswill be referred to The proportion of mixed alkylhalides employed with respect to the aromatic compound in thepreparation of the alkylated aromatic compounds may be varied.Preferably the proportion of mixed halogenated hydrocarbons employedwith respect to the aromatic compound is such that only one higher alkylradical is contained in the resulting alkyl aromatic compounds.- Thus,at least 1.25 mols oi aromatic compound per mol of mixed halogenatedhydrocarbons is ordinarily employed in the condensation. A molar ratioas low as 1 to 1 may be employed, but the yield of the resulting mixedalkyl aromatic compounds contalning'one long alkyl group will be less.

The sulphonation of themixture of alkyl aromatic compounds may becarried out with any suitable agent; as for example, sulphuric acids ofvarious strengths (66 Be, 100 per cent, 26 per cent oleum, 65 per centoleum, etc.), chlorsulphonic acid, etc. The sulphonation may be carriedout in the presence of inert solvents or diluents, as for example, thehalogenated aliphatic or aromatic hydrocarbons (carbon tetrachloride,tetrachlor ethane, ethylene dichloride, dichlorbenzene, etc.) orsulphonation may be carried out in their absence. When an inert solventor diluent is used, it may be separated mechanically or by evaporationfrom the alkaline aqueous solution of the sulphonic acid salts of thealkyl aromatic compounds which results upon diluting the sulphonationmass with water and adding an alkali. If desired, sulphonationassistants may be employed, as for example the lowerfatty acids andtheir anhydride (e. g., acetic acid, acetic anhydride, etc.) or thealkali metal sulphates (e. g., sodium or potassium sulphate, etc.)

The temperature at which the sulphonation is carried out may vary withinwide limits. For example, temperatures as low as about and as high asabout 140? may be employed. In general the more vigorous thesulphonation agent the lower is the preferred temperature. Preferredsulphonation temperatures lie between about 5 and about 90. g

The ratio of sulphonating agent employed with respect to the mixture ofalkyl aromatic compounds also may be varied. Thus, for completesulphonation, the sulphonating agent in terms of 100 per cent sulphuricacid may range from 0.3 to 5 times or more the weight of the alkylaromatic compounds to be sulphonated. The extent to which thesulphonation is carried out may vary with the individual material beingsulphonated, the duration or time of sulphonation, and the use to bemade of the sulphonated product. In some cases, a degree of sulphonationwhich corresponds with a product having maximum detergent properties isnot completely soluble in water to form a clear solution and/or maycause some precipitation of lime salts. On the other hand, a productwhich causes no precipitation of lime salts may not have maximumobtainable detergent properties because of excessive sulphonation.Furthermore, in some cases the degree of sulphonation may not be thesame for products to be used as detergents in soft water, in hard .watcrand in alkaline solutions. As a standard of comparison, an aqueoussolution of calcium chloride equivalent to 0.224 gram calcium oxide perliter of solution is employed as a standard hard water.)

The sulphonated products may be prepared in the form of their freesulphonic acids or in the form of salts. They are preferably prepared inaccordance with the present invention in the form of salts of the-alkalimetals. 'The salts may b obtained in any suitable manner; for example,by reacting the sulphonated product with a metal oxide or hydroxide,ammonia or an organic base, or of a suitable salt 01' one of these, inan amount adapted to form a neutral product. Among the bases, oxides andsalts which may be combined with the sulphonated products to producesalts in accordance with the present invention are, for example, sodium,potassium and ammonium hydroxides; sodium potassium and ammoniumcarbonates and bicarbonates: ammonia; magnesium oxide; ethylamine;pyridine; 'riethanolamine; propanolamines; butanolamin s; diaminopropanol; ethylene diamine; triethylene tetramine; aniline; o-toluidine;etc.

The reaction mixtures resulting from the sulphonation of themixed alkylaromatic compounds may also be directly employed for the formation ofmixed products, as for example, mixtures of salts of the alkyl aromaticsulphonic acids and other acids present in said reaction mixtures. Thus,the sulphonation reaction mixture resulting from the treatment of themixed alkyl aromatic compounds with an amount of sulphonating agent inexcess 01 that theoretically required to effect the desired degree ofsulphonation may be treated with a suitable inorganic or organic base orbasic salt (as for ex ample, one oi those mentioned) and the resultingmixture ofthe salts of the sulphonated alkyl aromatic compounds and theinorganic salt (as for example, sodium sulphate) may be jointly isolatedfrom the reaction mixture and employed as such. If it is desired toproduce salts or the sulphonated alkyl aromatic compounds in a formsubstantially free from inorganic salts (for example, inorganicsulphates) this may be accomplished by taking advantage of their greatersolubility than the inorganic salts in alcohol and other organicsolvents, or by using an amount 01' chlorsulphonic acid such that noexcess, or only a relatively small excess of it is present in the finalsulphonation mass or mixture.

I claim:

1. In the method of producing higher alkyl aromatic sulphonates fromnon-aromatic hydrocarbons and aromatic compounds of the class consistingof hydrocarbons, monochlor hydrocarbons, and alkoxy-substitutedhydrocarbons of the benzene and naphthalene series, by halogenation ofthe non-aromatic hydrocarbons, condensation of the allgvl halides withthe arc-- matic compound with the aid of aluminum chloride as acondensation catalyst, followed by sulphonation, the improvement whichcomprises halogenating the non-aromatic hydrocarbons to an extent suchthat the resulting halogenation reaction mixture contains an amount oforganically combined halogen substantially corresponding with 75 percent to 175 per cent complete monohalogenation oi the non-aromatichydrocarbons, condensing the resulting alkyl halide mixture with thearomatic compound and an amount of aluminum chloride equal to less than5 per cent of the alkyl halide mixture at a temperature not exceedingC., subjecting the resulting alkyl aromatic compounds to furthertreatment at a temperature not exceeding 130 C. with an additionalamount of aluminum chloride, the total amount of aluminum chloride being5 to 20 per cent of the alkyl halide mixture,

and separating the resulting alkyl aromatic compounds from the reactionproduct.

2. In the method of producing higher alkyl aromatic sulphonates fromnon-aromatic hydrocarbons and aromatic compounds of the class consistingof hydrocarbons, monochlor hydrocarbons, and alkoxy-substitutedhflfocarbons of the. benzene and naphthalene series, by chlorination ofthe non-aromatic hydrocarbons, condensation of the alkyl chlorides withan aromatic compound with the, aid of aluminumjcilorideaas acondensation catalyst, followed by sulphona- .tion, the improvementwhich comprises chlorinating the non-aromatic hydrocarbons to an extentsuch that the resulting chlorination reaction mixture contains an amountof organically combined chlorine substantially corresponding with 75 percent to 1'75 per cent complete monochlorination of the non-aromatichydrocarbons, condensing the resulting alkyl chloride mixture with thearomatic compound and an amount of aluminum chloride equal to not morethan 4 per cent of the alkyl chloride mixture at a temperature notexceeding 130 C., subjecting the resulting alkyl aromatic compounds tofurther treatment at a temperature not exceeding 130 C. with anadditional amount of aluminum chloride, the total amount of aluminumchloride being 5 to 20 per cent of the alkyl chloride mixture, andseparating resulting alkyl aromatic compounds from the reaction product.

3. In the method of producing higher alkyl benzene sulphonates fromnon-aromatic hydro-- carbons and benzene by chlorination of thenonaromatic hydrocarbons, condensation of the alkyl chlorides withbenzene with the aid of aluminum chloride as a condensation catalyst,followed by sulphonation, the improvement which comprises chlorinating apetroleum hydrocarbon distillate containing to 30 carbon atoms to anextent such that the resulting chlorination reaction mixture contains anamount of organically combined chlorine substantially corresponding with75 per cent to 175 per cent complete monochlorination, condensing theresulting alkyl chloride mixture with benene and an amount of aluminumchloride equal to less than 5 per cent of the alkyl chloride mixture ata temperature not exceeding 130 C., subjecting the resulting alkylbenzene compounds to further treatment at a temperature not exceeding130 C. with an additional amount of aluminum chloride, the total amountof aluminum chloride being 5 to per cent of the alkyl chloride mixture,and separating resulting alkyl condensation compounds from the reactionproduct.

4. The method of producing sulphonated prod ucts having surface activeproperties, which comprises chlorinating a petroleum hydrocarbondistillate containing 10 to 30 carbon atoms to an extent such that theresulting chlorination reaction mixture contains an amount oforganically combined chlorine substantially corresponding with '75 percent to 175 per cent complete monochlorination of the hydrocarbonmixture, condensating the resulting alkyl chloride mixture with anaromatic hydrocarbon of the benzene and naphthalene series at atemperature not exceeding 130 C. in the presence of an amount ofanhydrous aluminum chloride equal to less than 5 per cent of the alkylchloride mixture, separating the resulting condensation product from thereaction product, subjecting the condensation product to furthertreatment at a temperature not exceeding 130 C. with an additionalamount of anhydrous aluminum chloride, the total amount of aluminumchloride being 5 to 20 per cent of the alkyl chloride mixture,separating resulting mixed alkyl aromatic compounds from the sludgeformed as a by--product of the treatment, and sulphonating resultingmixed alkyl aromatic compounds.

5. The method of producing sulphonated products having surface activeproperties, which comprises chlorinating a petroleum hydrocarbondistillate containing 10 to 30 carbon atoms to an extent such that theresulting chlorination reaction mixture contains an amount oforganically combined chlorine substantially corresponding with 75 percent to 175 per cent complete monochlorination of the hydrocarbonmixture, condensating the resulting alkyl chloride mixture densationproduction to further treatment at a temperature between 20 and C. withan addi-. tional amount of anhydrous aluminum chloride,

the total amount of aluminum chloride being 5 to 20 per cent of thealkyl chloridegnixture, separating resulting mixed alkyl aromaticcompounds from the sludge formed as a by-product of the treatment,subjecting the resulting mixed alkyl aromatic compounds to distillationto remove lower boiling substances than the alkyl aromatic compounds,and sulphonating resulting mixed alkyl aromatic compounds.

- 6. The method of producing sulphonated products having surface activeproperties, which comprises chlorinating a petroleum hydrocarbondistillate containing 10 to 30 carbon atoms to an extent such that theresulting chlorination reaction mixture contains an amount oforganically combined chlorine substantially corresponding with 75 percent to 75 per cent complete monochlorination, condensing the resultingalkyl chloride mixture with benzene in the presence'of anhydrousaluminum chloride in an amount equal to less than 5 per cent of theweightoi the alkyl chloride mixture at a temperature not exceeding C.,separating the resulting alkyl benzene mixture from the sludge formed asa by-product of the reaction, subjecting the alkyl benzene mixture tofurther treatment at a temperature not exceeding 130 C. with anadditionalamount of anhydrous aluminum chloride, the total amount ofaluminum chloride being-5 to 20 per cent of the alkyl chloride mixture,separating resulting mixed alkyl benzenes from the sludge formed as aby-product of the treatment, subjecting the resulting mixed alkylbenzenes to distillation to remove lower boiling substances than thealkyl benzene, and sulfonating the alkyl benzenes.

7. The method ofproducing sulphonated products having surface activeproperties, which comprises chlorinating a petroleum hydrocarbondistillate containing 10 to 30 carbon atoms to an extent such that theresulting chlorination reaction mixture contains an amount oforganically combined chlorine substantially corresponding with 75 percent to 1'75 per cent complete monochlorination, condensing theresulting alkyl chloride mixture with benzene in the presence ofanhydrous aluminum chloride in an amount equal to less than 5 per centof the weight of the alkyl chloride mixture at a temperature notexceeding 130 C., separating the resulting condensation product from thesludge formed as a by-product of the reaction, distilling residualbenzene from the condensation product, subjecting the resultingcondensation product to further treatment at a temperature not exceeding130 C. with an additional amount of anhydrous aluminum chloride, thetotal amount .of aluminum chloride being to 20 per cent of the alkylchloride mixture, separating the resulting alkyl benzene mixture fromthe sludge formed as a by-product of the treatment, subjecting the alkylbenzene mix ture to vacuum distillation to remove lower boilingsubstances than the alkyl benzenes, and suli'onating the remaining alkylbenzene mixture.

8. The method of producing sulphonated products having surface activeproperties, which comprises chlorinating a paraflinic petroleumhydrocarbon distillate containing 12 to 30 carbon atoms to an extentsuch that the resulting chlorination reaction mixture contains an amountof organically combined chlorine substantially corresponding with 100per cent to 140 per cent complete monochlorination, condensing theresulting alkyl chloride mixture with benzene at a temperature between20 and 80 C. in the presence of anhydrous aluminum chloride in an amountequal to less than 5 per cent of the alkyl chloride mixture, separatingthe resulting condensation product from the sludge formed as aby-product of the reaction, subjecting the condensation product tofurther treatment at a temperature between 20 and 80 C. with anadditional amount of anhy drous aluminum chloride, the total amount ofaluminum chloride being 5 to 20 per cent of the alkyl chloride mixture,separating the resulting alkyl benzene mixture'from the sludge formed asa by-product of the treatment, subjecting the alkyl benzene mixture tovacuum distillation to remove lower boiling substances than the alkylbenzenes, and sulphonating the remaining alkyl benzene mixture.

9. The method of producing sulphonated products having surface activeproperties, which comprises chlorinating a parafiinic petroleumhydrocarbon distillate of the Pennsylvania type containing 12 to 30carbon. atoms to an extent such that the resulting chlorination reactionmixture contains an amount of organically combined chlorinesubstantially corresponding with 100 per cent to 140 per cent completemonochlorination, condensing the resulting alkyl chloride mixture withbenzene at a temperature between 20 and 80 C. in the presence ofanhydrous aluminum chloride in ,an amount equal to not more than 4 percent of the alkyl chloride mixture, separating the resultingcondensation product from the sludge formed as a by-product of thereaction, distilling residual benzene from the condensation product,subjecting the condensation product to further treatment at atemperature between 20 and 80 C. with an additional amount or anhydrousaluminum chloride, the total amount of extent such that the resultingchlorination reaction mixture contains an amount of organically combinedchlorine substantially corresponding with per cent to 1'75 per cent com-.plete monochlorination of the hydrocarbon mixture, condensing theresulting alkyl chloride mixture with an aromatic hydrocarbon of thebenzene and naphthalene series at a temperature between 20 and C. in thepresence of an amount of anhydrous aluminum chloride equal to not morethan 4 per cent or the alkyl chloride mixture, subjecting thecondensation product to further treatment at a temperature between 20and 80 C. with an additional amount of anhydrous aluminum chloride, thetotal amount of aluminum chloride being 5 to 20 per cent of the alkylchloride mixture, separating a resulting liquid product containing mixedalkyl aromatic compounds from the sludge formed as a by-product of thetreatment, subjecting the separated liquid product to distillation toremove lower boiling substances than the alkyl aromatic compounds, andsulphonating the mixed alkyl aromatic compounds.

11. The method of producing sulphonated products having surface activeproperties, which comprises chlorinating a parafllnic petroleumhydrocarbon distillate containing 12 to 30 carbon atms to an extent suchthat the resulting chlorination reaction mixture contains an amount oforganically combined chlorine substantially corresponding with per centto per cent complete monochlorination, condensing the resulting alkylchloride mixture with benzene at a temperature between 20 and 80 C. inthe presence of anhydrous aluminum chloride inan amount equal to lessthan 5 per cent of the alkyl chloride mixture, subjecting thecondensation product to further treatment at a temperature between 20and 80 C. with an additional amount of anhydrous aluminum chloride, thetotal amount of aluminum chloride. being 5 to 20 per cent of the alkylchloride mixture, separating a resulting liquid product containing amixture of alkyl benzenes from the sludge formed as a lay-product of thetreatment, subjecting the separated liquid product to vacuumdistillation to remove lower boiling substances than the alkyl benzenes,and sulphonating resulting alkyl benzenes.

LAWRENCE H.

CERTIFICATE OF commoner. Patent-No. 2,51h,929. March 50, 19!;5.

LAWRENCEH. mm.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 5,first column, line 2, for "detergnet'" read --detergent--; and secondcolumn, line 65, for "80 c." read --2o c.--; page 7,1irst column, line11.6, claim 3,

for "oenene" read --benzene-; line 65-66, claim 11., And second column,line 16-17, claim 5, for condensating read "condensing"; line 25, claim5, for "production" read -product--; and that the said Letters Patentshould be read with this correction therein that the same may conform tothe record of the case in the Patent office.

Signed and sealed this 18th day of May, A. n. 1915.

Henry Van Arsdale,

(Seal) Acting Commissioner of Patents.

